全文获取类型
收费全文 | 3331篇 |
免费 | 94篇 |
国内免费 | 10篇 |
专业分类
化学 | 2092篇 |
晶体学 | 23篇 |
力学 | 63篇 |
数学 | 363篇 |
物理学 | 894篇 |
出版年
2022年 | 24篇 |
2021年 | 25篇 |
2020年 | 53篇 |
2019年 | 41篇 |
2018年 | 27篇 |
2017年 | 24篇 |
2016年 | 52篇 |
2015年 | 65篇 |
2014年 | 63篇 |
2013年 | 126篇 |
2012年 | 127篇 |
2011年 | 148篇 |
2010年 | 95篇 |
2009年 | 98篇 |
2008年 | 159篇 |
2007年 | 139篇 |
2006年 | 126篇 |
2005年 | 146篇 |
2004年 | 110篇 |
2003年 | 92篇 |
2002年 | 92篇 |
2001年 | 66篇 |
2000年 | 67篇 |
1999年 | 47篇 |
1998年 | 35篇 |
1997年 | 39篇 |
1996年 | 54篇 |
1995年 | 53篇 |
1994年 | 63篇 |
1993年 | 79篇 |
1992年 | 66篇 |
1991年 | 44篇 |
1990年 | 48篇 |
1989年 | 48篇 |
1988年 | 37篇 |
1987年 | 46篇 |
1986年 | 46篇 |
1985年 | 40篇 |
1984年 | 43篇 |
1983年 | 35篇 |
1982年 | 34篇 |
1981年 | 43篇 |
1980年 | 41篇 |
1979年 | 37篇 |
1978年 | 35篇 |
1977年 | 39篇 |
1976年 | 40篇 |
1974年 | 24篇 |
1973年 | 41篇 |
1970年 | 23篇 |
排序方式: 共有3435条查询结果,搜索用时 15 毫秒
91.
The rate of nucleation of calcium hydroxide in carefully purified supersaturated solution was observed to be about 10(3) particles, cm(-3). sec(-1), in solutions with activity products a(ca)a(OH)(2) around 4 x 10(-5). These data correspond to a homogeneous nucleus containing about 55Ca(OH)(2) units, and a nucleus-solution interfacial tension of 65 erg cm (2). 相似文献
92.
Arsenic speciation is of increasing interest to the food industry, as concerns about high total arsenic concentrations in
food can often be alleviated to a great extent if the ratio of toxic, less toxic and non-toxic arsenic compounds in the sample
is known.
The lipid matrix of fish oil is a challenge in the determination of arsenic species, as current methods for this type of analysis
require the analyte to be water-soluble. In this study, two sample preparation techniques were applied. One the one hand water-soluble
species were extracted with methanol/water, on the other, acid digestion was applied to release lipid-soluble arsenic compounds
into the aqueous phase. Ion chromatography – inductively coupled plasma mass spectrometry (IC-ICP-MS) was used for separation
and sensitive element-specific detection of arsenic compounds. Additional experiments, including alkaline hydrolysis, were
carried out to find out more about the type of lipids arsenic is bound to in fish oil.
Up to eight different arsenic species were detected and quantified in fish oil with dimethylarsinate being the major compound
both in the aqueous extract and in the acid digest. No inorganic arsenic was detected in the aqueous extract, and the maximum
concentration of arsenate determined in the acid digest was 0.05 μg g−1.
The total arsenic concentration determined by ICP-MS ranged from <0.1 to 5 μg g−1. With regard to the mass balance, approximately 1% of the total arsenic content was extractable with methanol/water, whereas
the sum of arsenic species quantified after acid digestion yielded 85–100% of the total arsenic content. It was confirmed
that the large fraction of arsenic in fish oil not extractable on an aqueous basis consists of organoarsenic compounds.
This new approach in sample preparation makes the complete characterization of the arsenic content in the sample possible
with regard to the respective species, providing necessary information required for risk assessment. 相似文献
93.
Summary A polystyrene sample obtained by free radical polymerization has been fractionated by preparative scale GPC and the structure and morphology of the fractions have been studied by13C-NMR spectroscopy, DSC and X-ray measurements. No changes in morphology in the course of fractionation have been obeyed. A distribution of syndiotacticity within the molecular weight distribution does not exist.
List of abbrevations and symbols AIBN a, a-Azo-bis-(iso-butyronitrile) - D Dispersity, M w /M n - DSC Differential scanning calorimetry - EF Efficiency of fractionation - GPC Gel permeation chromatography - m mass of the fraction - M mass of the fractionated polymer sample - MWD Molecular weight distribution - P r content of racemic dyads - PS Polystyrene - THF Tetrahydrofuran - U D-1 - U ss U of the starting sample - U f U of the fraction Auszug aus der Dissertation von U.-D. Standt: Zur Morphologie von Polystyrol, TU Braunschweig 1981. 相似文献
Zusammenfassung Eine Polystyrolprobe, die durch radikalische Polymerisation hergestellt wurde, wurde mit Hilfe der präparativen Gelpermeationschromatographie fraktioniert; die Struktur und Morphologie der Fraktionen wurde mit13C-NMR-Spektroskopie, DSC und Röntgenbeugung untersucht. Im Verlauf der Fraktionierung traten keine Änderungen der Morphologie der Fraktionen auf. Innerhalb der Molekulargewichtsverteilung existiert keine Verteilung der Syndiotaktizität.
List of abbrevations and symbols AIBN a, a-Azo-bis-(iso-butyronitrile) - D Dispersity, M w /M n - DSC Differential scanning calorimetry - EF Efficiency of fractionation - GPC Gel permeation chromatography - m mass of the fraction - M mass of the fractionated polymer sample - MWD Molecular weight distribution - P r content of racemic dyads - PS Polystyrene - THF Tetrahydrofuran - U D-1 - U ss U of the starting sample - U f U of the fraction Auszug aus der Dissertation von U.-D. Standt: Zur Morphologie von Polystyrol, TU Braunschweig 1981. 相似文献
94.
T.
ivkovi M. Randi D. J. Klein H.-Y. Zhu N. Trinajsti 《Journal of computational chemistry》1995,16(4):517-526
We consider rigorous evaluation of conjugated-circuit resonance energies for families of structurally related benzenoid hydrocarbons of increasing size. Local and global aromatic properties of such molecules are investigated with particular interest in modeling high polymers. Using the algebra of large numbers, exact formulas for contributions from individual benzene rings of polymers with up to 25,000 repeating units (close to half a million carbon atoms) were derived. All arithmetic procedures were carried out in terms of whole numbers retaining all digits, of which there were sometimes more than 105. © 1995 by John Wiley & Sons, Inc. 相似文献
95.
Abstract— The influence of excitation wavelength, pH, oxygen and solvents, upon fluorescence quantum yields, were measured for insole Indole in neutral aqueous solution exhibits the same wavelength dependence as tryptophan, which indicates that COO- absorption is not responsible for the effect. Parameters such as pH and oxygen influence only the absolute fluorescence quantum yields but not their relative variation with wavelength, indicating competition with fluorescence emission for S1 deactivation. without any influence upon deactivation of higher excited states. In contrast, solvents exhibit a specific influence upon the wavelength dependence; for indole, the decrease of fluorescence yield excited around 215 nm, compared with the yield in the first absorption band is about 40% in water, 10% in acetonitrile, 70% in n-hexane and cyclohexane, whereas no appreciable decrease occurs in methanol, ethanol or n-butanol. These observations, together with the Stokes shifts of the emission spectra, may be well correlated with Kosower's Z-values, expressing microscopic solvent-solute interactions. 相似文献
96.
Pyell U 《Journal of chromatography. A》2004,1037(1-2):479-490
The determination of the velocities of the mobile and the pseudostationary phases (the migration (time) window) is mandatory for the determination of physicochemical properties by electrokinetic chromatography (EKC). This review offers a detailed discussion on the definition, the importance, the determination and the regulation of the migration (time) window in EKC. An overview on the theoretical treatment of chromatographic processes in EKC is given defining EKC in comparison to the term capillary electrophoresis. Methods to determine and influence the migration window are discussed with emphasis on measures that have been taken to modify the electroosmotic flow velocity. Pseudostationary phases (or separation carriers) that are taken into consideration are anionic and cationic micelles, mixed micelles, microdroplets (microemulsions), polymeric pseudostationary phases and dendrimers. 相似文献
97.
Zhi L Gorelik T Wu J Kolb U Müllen K 《Journal of the American Chemical Society》2005,127(37):12792-12793
Novel naphthalocyanine (Nc) nanotubes with special wall structures were fabricated by a template method using Nc molecules as building blocks. Thermal stabilization of the ordered columnar structures of the tetrakis(tert-butyl)naphthalocyanine (Ni-BNc) molecules, induced from the pi-pi interactions in the nanoscale channels of an alumina template, resulted in Nc nanotubes with walls consisting of well-ordered Nc molecular disks. Further thermal treatment of Ni-BNc at 600 degrees C produced carbonized Nc nanotubes containing ordered columnar, graphitic wall structures with the graphene disks arranged perpendicular to the tube axis. These nanotubes may be useful for extending the application of Nc molecules for nanodevice fabrication. 相似文献
98.
Bing H. Wang Klaus Dreisewerd Ute Bahr Michael Karas Franz Hillenkamp 《Journal of the American Society for Mass Spectrometry》1993,4(5):393-398
The ionization mechanisms involved in matrix-assisted ultraviolet laser desorption/ionization (MALDI) were studied with a time-of-flight mass spectrometer. When protonated or cationized quasimolecular ions generated by MALDI are not extracted promptly, their abundance is a function of the delay time between laser irradiation and ion extraction, maximizing at an optimum delay time (DTM) of a few hundred nanoseconds. The ion abundance at DTM exceeds that of prompt extraction by a factor of 2 or more. Increasing the cation density near the sample surface reduces the DTM, whereas increasing the desorption laser irradiance has the opposite effect. The enhancement suggests extensive gas-phase ion-molecule reactions after irradiation by the desorption laser has ceased. 相似文献
99.
Michael Klein 《Tetrahedron》2004,60(5):1087-1092
The synthesis of an enediyne sulfonamide by alkylidene carbene rearrangement is reported. The compound cyclizes thermally to give the Bergman product, which was prepared independently for comparison. Like other σ-acceptor substituents at the enediyne alkyne termini, such as fluoride, oxonium or ammonium groups, the sulfonamide moiety enhances the reactivity for thermal Bergman cyclization as shown by the cyclization kinetic of the title compound. 相似文献
100.
Heinz-Peter Klein Ulf Thewalt Karl Döppert Roberto Sanchez-Delgado 《Journal of organometallic chemistry》1982,236(2):189-195
The trinuclear titanium(IV) complex (π-C5H5)2TiClOTi(π-C5H5)ClOTiCl(π-C5H5)2 · CHCl3 is formed by hydrolysis of (π-C5H5)2TiCl2 at pH > 3.5 and can be isolated in the crystalline state from the reaction of (π-C5H5)2TiCl2 with Ag2O and water in chloroform. Its structure is determined by X-ray analysis. 相似文献